TY  - JOUR
AU  - Tomaník, Lukáš
AU  - Pugini, Michele
AU  - Mudryk, Karen
AU  - Thuermer, Stephan
AU  - Stemer, Dominik
AU  - Credidio, Bruno
AU  - Trinter, Florian
AU  - Winter, Bernd
AU  - Slavicek, Petr
TI  - Liquid-jet photoemission spectroscopy as a structural tool: site-specific acid–base chemistry of vitamin C
JO  - Physical chemistry, chemical physics
VL  - 26
IS  - 29
SN  - 1463-9076
CY  - Cambridge
PB  - RSC Publ.
M1  - PUBDB-2024-05395
SP  - 19673-19684
PY  - 2024
N1  - Open Access
AB  - Liquid-jet photoemission spectroscopy (LJ-PES) directly probes the electronic structure of solutes and solvents. It also emerges as a novel tool to explore chemical structure in aqueous solutions, yet the scope of the approach has to be examined. Here, we present a pH-dependent liquid-jet photoelectron spectroscopic investigation of ascorbic acid (vitamin C). We combine core-level photoelectron spectroscopy and ab initio calculations, allowing us to site-specifically explore the acid–base chemistry of the biomolecule. For the first time, we demonstrate the capability of the method to simultaneously assign two deprotonation sites within the molecule. We show that a large change in chemical shift appears even for atoms distant several bonds from the chemically modified group. Furthermore, we present a highly efficient and accurate computational protocol based on a single structure using the maximum-overlap method for modeling core-level photoelectron spectra in aqueous environments. This work poses a broader question: to what extent can LJ-PES complement established structural techniques such as nuclear magnetic resonance? Answering this question is highly relevant in view of the large number of incorrect molecular structures published.
LB  - PUB:(DE-HGF)16
C6  - 38963770
UR  - <Go to ISI:>//WOS:001261898700001
DO  - DOI:10.1039/D4CP01521E
UR  - https://bib-pubdb1.desy.de/record/612577
ER  -